Method



APPLICATION FILED JULY 22.1913.

Patented Mar. 7, 192

q vi cmaoeo a direct and economical method for t UNITED STATES PATENT OFFICE.

GASBEB W- MILES, OF ANDERSON TOWNSHIP, HAMIIAON COUNTY, OEIQ METHOD OF NITROGEN FIXATION.

1*,408Ji25, Specification of Letters Patent. Patent d f '1 1922 cation filed July 22, 1918. Serial no. 246,222.

To;all whom it may cancer-m. A as circulati um 6 is desi ed to -Be it known that I, CASPER W. MILES, a suppl practicall y li ure nitrogen or citizen of the United States, residin at Another nitrogen containing gas, as or inderson Township, in the county 0 Hamilstance'mixed hydrogenand nitrogen gas or ton and State of Ohio, have invented cernitrogen mixed with a chemicall finerts ltainnew and useful Improvements in Methfree from oxygen, to one of t e fixation ads of Nitrogen Fixation, of which the following is a specification. 1 "M yinvention relates to im rovements in method and apparatus for t e fixation of nit-rogen. One of its objects is to provide e fixation of nitrogen. Another'object is to provide amethod of fixation whereby rectically pure products may be direct y obtained. Another object is to provide for the combined action of a plurality of forces all tendingto the fixation of nitrogen. An-

.other object is to provide an improved method for the production of ammonia and nitric acid separately, and also the product of their chemical union. Another object is to provide improved apparatus to carry out said method. M invention also comprises certain details 0t method-and combination and details of a paratus, all of which will be ,fully set forth in the description of the accompanying drawings, in wh1ch:

Fig. 1 1s a diagrammatic illustration of apparatus suitable to carry out my improved method, with the production as an end product of ammonium nitrate.

Fig. 2 is a diagrammatic illustration of a modification of a portion of said apparatus for the production of nitric acid andammonia as end products.

in the accompanying drawings 4 represents a gas circulating pump to supply air or nitrogen gas received through conduit 3 to a nitrogen fixation'chamber, A gas C11- ulatingpump 5 is desi ned to supply oxygen gas received througi a condu1t2 to the seine fixation chamber as the product of pum l. The pumps 4 and 5 may be ind-epent ently driven at relatively different speeds, but are illustrated as driven in unison from a common shaft f by means of a belt wheel or gear wheel h, and provision is made to adjustably vary the stroke and length of the connecting rods of said pumps so that therelative amountof gas pumped or circulated by the respective pumps may be accurately adjusted or predetermined to secure any desired proportion of oxygen and nitrogen in the mixture circulated to the fixation chamber.

chambers from a store e gasomete'r 7 through a conduit 7'. T e supply to the gasometer 7 may be the gaseous product of combustion freed. from carbonic acid gas, or nitrogen from other sources.

The gas circulating pump 8 is designed to supply hydrogen as through conduit 9 to the samefixation c amber as the product of pump 6, and the pumps (iand 8 are preferably ad ustable as described for pumps 4 and 5 to enable any desired ratio of mtrm gen and hydrogen to be mixed and pumped together to a fixation chamber;

An electrolytic cell 10, or a battery of any desired number of such cells, is preferably the pump 5 through conduit 2 andafrom the,

pump ough conduit 16 to conduit 15 where the two' gases are intimately mixed in the desired proportions to produce a mixture rich in oxygen and referably containing two or more parts 0 oxygen to one of nitrogen, depending upon the operating conditions. This mixture is conducted-by conduit 15 to a fixation chamber 1 8 the lower portion of which is occupied by a body of iquid 17, as for instance water, which liquid is made one pole terminal or eleotroddof a high tension unidirectional electric current- The other pole or terminal 19 is located within the chamber 18 and insulated therefrom, being suspended in the oxygen enriched gas in said chamber, and is provided with one or more points 19' from which either spark or silent electrical discharge may he directed throu her 18 to the face of t 1e liqu'ad, terminal, or electrode 17.

Hydrogen gas circulated by pump 8, and nitrogen gas circulated by the pump 6 thro'u cham er he required in said through the conduit 7 from gasometer 7 are intimately mixed in the conduit 20 and thence enter the fixation chamber-20' above e (apposite section or leg of the "body of li A partition 21 separates thetwo legsthe li uid in the lower portion of the fixation c amber so that the body of liquid is U-shaped in cross-section with one end or surface in contact with mixed nitrogen and ox gen in chamber 18, andthe other end or sun ace in contact with mixed nitrogen and hydrogen in chamber 20. An electrdde or pole 22 is admitted through and insulated from the walls of, chamber 20 andhas one or more points 22 from which either spark or silent electrical discharge me be directed upon the surface of the liqui 17 h the mixed hydrogen and nitrogen in keepiiilg the liquid in said chamber at any desiretemperature below its boiling or extensive vaporizijtion temperature. Artificial refrigeration why if desired be employed to coolthe coil 27. A pipe connection 28 enables a portion ofthe liquid to be withdrawn for the purpose of recovering the product and replacing it with fresh liquid. The pipe connection 28 also provides for varying or adjusting the surface level of the liquid 17 by adding to or removing a portion of the liquid17 throughthe pipe connection 28. Coil 27 is immersed in a tank 29 of cooling medium. I

A gas exit conduit 30 leads from the chamber 20' to a storage gasometer 31 through a liraiirfh'conduit 32. while the branch 33 may ."bi employed to supply mixed nitrogen and hydrogen to the fixation chamber 20 of one or more additional fixation elements surh as illustrated in Fig. 1, and in which the gas; ometer 31 serves to maintain a uniform gas pressure and gas supply. I also preferably provide an exit cock from the last of said fixation chambers whereby :1 small per- .centage of gas may be bled and wasted or stored for other purposes. which serves to eliminate from the fixation chambers :20 and gasometer 31 any gas impurities \Vllll'li may slowly accumulate therein. A conduit 35 is employed in like manner to the conduit 3 to lend mixed nitrogen and oxygen gas from the chamber 18 to a storage gasometer and [he fixation chambers of other fixation Pllfllilils xation chamber, and

as heretofore described for conduits 30, 32 and 33, and including an exit cock to lead away accumulating as impurities.

The effect of the g'h; tension unidirectional current of circuit 24a to polarizothe two end surfaces of the-liquid 17 oppositely to the polarizing eifect exerted by saidcircuit at the electrodes 19' and 22' so that to a greater or less extent nascent oxygen appears at the surface of the liquid'mchamber 18 and hydrogen in nascent state appeers at the surface of the liquid in chimiber 20', while the gases ins the respective chambers are subjected b the current to an ionizin effect, a, local eating efiect, and a polarizing or electrolytic effect tending to bring nascent ox gen in chamber 18 at the liquid 17 so as-to e ect a separation of the fixednitrogen from the unfixed nitrogen-and gases mixed therewith in the respective chain.- hers, leaving the mixed gases practicallypure or free from fixation products, andiin condition to undergo the fixation operation free from complications. The fixation products-from the respective fixation chambers promptly enter into chemical union one with the other to produce ammonium nitrate in solution in the liquid 17 from which it is removed and recovered from time to time,-or

by a continuous operation. The oxygen enl'ichrnent of the nitro on gas, the solution energy or tendenc o the liquid, and the chemical combinationenergy, all tend to a fixation of nitrogen with oxygen with an exothermic result. In a similar manner the reciprocal tendencies of nitrogen and hydrogen to combine and disassociate, and to establish an equilibrium between the ammonia and mixed gasesis upset by the solution tendency or capacity of the liquid, thereby maintaining aconstant potential toward the extensive formation of ammonia by its rapid absorption and removal, which is fun ther facilitated by the tendency of the ammonia to chemically combine with the nitric acid products, which also prevents the liquid from becoming even partially saturated with ammonia in solution. Gases from sources other than electrolytic may be fed to chambers l8 and 20'.

The container or containers for the liquid 1? requi e to be of insulating material, and of rheiiiloel resisting nature. as for instance ol glass or pmrciuin. and the apparatus for cooling the liquid 17 requires to be suitably insulated one unit from another to provide for conducting the high tension current along the prescribed path or circuit. -It is not requisite that the high tension circuit should be strictly unidirectional, but the flow 0t current over a unit of time should predominate in one direction to provide the desired polarity at the surfaces of the liquid- 17. The primary object of the high tension currentis to maintain an ionizing, polarizing and local heatin efiect as distin 'ished from a purely electro ytic effect, but t e electrolytic efl'ect maybe varied within considerable limits, as may also the rapidity or mass of the reaction'in the fixation chamber. The electrodes 19 and 22' may be composed of metals resistant to the chemical reactions and substances present, or of non-metallic conductors having the necessary chemical resistin properties. Gas pressures in the fixation c ambers may either above or below atmospheric ressure.

In the mo ification Fig. 2, the fixation is.

carried on in two independent chambers or chamber sections. In section 40 is a mixture ofnitrogen and oxy en gas, a liquid 41 and.

a suspended electro e42, and liquid circulatin conduits .43 and 44 for cooling and circu atin the liquid, and gas supply and exit con uits 45 and 4. Nitric acid is formed in chamber 40 an may be recovered as nitric acid. Chamber 47 contains a mixture of nitrogen and by rogen gas, a'liquid 48 and sus enud electrode 48, and has liquid circu ating and cooling conduits 49.

and 50, and gas supply and exit conduits 51 and 52. Ammonia gas is formed in chamber 47 and is absorbed in the liquid 48 and recovered as ammonia. An insulated electric condiictor 53 serves to conduct the high tension current of unidirectional electrical circuit 54 firom one of the liquids 41 and 48 to the 0 her. The electrolytic effect at the o ends of electrode 53 would ordinari y osi relatively small, but may if desired be masked by a porous division or other means so asnot to act electrolytically directly upon the fixation products. An X within a circle indicate the several controlling valves in the respective conduits.

The apparatus herein illustrated may be exte'i'isively modified and is designed merely to illustrate a means for carrying the method into effect. The method is capable of considerable modification without departing from the principle of my invention.

\Vhat I claim is:

l. The method of nitrogen fixation comprising producing oxygen gas and hydrogen gas electrolytically, mixing said oxygen gas with'nitrogen gas in one fixation chamber, mixing said hydrogen gas with nitrogen gas in a separate fixation chamber, and independently fixingsaid oxygen gas and by drogen gas with nitrogen to each produce a nitrogen compound.

2. he met od of nitrogen fixation comprising producing oxygen gas and hydrogen gas electrolytically, feeding said oxygen gas and nitrogen gas as a mixture in predetermined proportions to a fixation chamber, feeding said hydrogen gas and nitrogen gas as a mixture in predetermined proportions to a separate fixation chamber, and independenty fixing said oxygen gas and hy drogen gas with nitrogen to each produce a nitrogen com ound.

3. he met 0d of nitrogen fixation comprising producin oxygen gas and hyd ogen gas electrolytical mixing said oxygen gas with atmospheric air in one fixation chamher to provide a gas mixture of high oxygen contents, mixing said hydrogen gas with nitro en gas in a separate fixation chamber,

and independently fixing said oxygen gas andv hydrogen gas with nitrogen to each proing said gas mixtures in the respective fixation chambers to electric currents of high tension in the presence of a liquid adapted to absorb the fixation product.

6. The method of nitrogen fixation com-m prising producin oxygen gas and hydrogen gas electrolytical y, mixing said oxygen gas withnitroigen gas in one fixation chamber, mixing said hydrogen gas with nitrogen gas .in a separate fixation chamber, and subjecting said gas mixtures in the respective fixation chambers in the presence of a liquid to electric currents of high tension in which current of one polarity predominates.

7. The method of electrolytic synthesis which comprises passing an electrolyzing electric current through an electrolyte, and respectively through a confined gaseous bod y at each terminal of said electrolyte.

8. The method of nitrogen fixation (runprising mixing oxygen gas with nitrogen gas in onefixation chamber, mixing hydrogen gas with nitrogen gas in a separate fixation chamber, and subjecting said gas mixtures in the respective fixation chambers to electric current of high tension.

9. The method of nitrogen fixation comprising mixing oxygen gas ith nitrogen the xation product.

as in one fixation chamber, mixing hyogen gas with nitrogen gas in a separate fixation chamber, and subjecting said gas mixturesin the respective fixation chamhere to electric current of high tension in the 'resence of a liquid adapted to absorb 10..The method of nitrogen fixation comrising mixing oxygen gas and nitrogen gas in one fixation chamber, mixing hydrogen "gas and nitrogen gas in a separate fixation A chamber, and subjecting said gas mixtures in the respective fixation chambers in the presonce of a liquid to electric current of, high tension in which current of one polarity predominates.

ment constitutes one electrode in contact with the gaseous mixture.

12. The method of nitrogen fixation comprising introducing a mixture of oxygen gas and nitrogen gas in which the oxygen gas exceeds in proportion that normally found in the atmosphere under substantially uniform pressure to one fixation chamber, introducing a mixture of hydrogen gas and nitrogen gas substantially free from exygen to a separate fixation chamber under substantially uniform pressure, and subjecting,

said gas mixtures in the respective fixation chambers to electric current of high tension in the presence of a liquid adapted to absorb the fixation product.

13. The method of nitrogen fixation comprising introducing a mixture of oxygen and nitrogen gas under substantially uniform pressure into one fixation chamber, introducing a mixture of hydrogen gas and nitrogen gas under substantially uniform pressure to a separate fixation chamber under substantially uniform pressure, and subjecting said gas mixtures in the respective fixation chambers to electric current of high potential in which current of one polarity predominates.

14. The method of nitrogen fixation comprising introducing a mixture of oxygen gas and nitrogen gas to one fixation chamber introducing a mixture of hydrogen gas and nitrogen as to aseparate fixation chamber, and su jecting said gas mixtures in the respective fixation chambers to electric current of high tension in the presence of a liquid adapted to absorb the fixation product, and maintaining a substantially unifoirm temperature in said absorbing iiqui I 15. The method of nitrogen fixation comprising introducing a mixture of oxygen'gas and nltrogeii gas to one fixation chamber introdueing a mixture of hydrogen gas and nitrogen gas into a separate fixation chamber, subjecting said gas mixtures in the respective fixation chambers to electric current of high tension in which current of one polarity predominates and in the presence of a liqui adapted to absorb thefixation prodnot, and maintaining said absorbing liquid at a substantially uniform temperature.

16. The method of nitrogen fixation com prising circulating a mixture of oxygen gas and nitro en gas through one fixation chamber, circu ating a mixture of hydrogen gas and nitrogen gas through a separate: fixation chamber, subjecting said gas mixtures in the respective fixation chambers to electric current of high tension in which current of one polarity predominates and in thepresence of aliquld adapted to absorb the fixation product, and maintaining the absorbing liquid at a substantially uniform temperature. 17. The method of nitrogen fixation comprising circulatinga mixture of oxygen gas and nit-r0 11 gas through one fixation chamber, circu ating a mixture of hydro en gas and nitrogen gas through a separatefixation chamber, subjecting said gas mixtures in the respective fixation chambers in the presence of a medium to absorb the fixation product to electric current ofhigh'tension.

18. The method of nitrogen fixation comprising mixing oxygen gas and nitrogen gas in one fixation chamber, mixing hydrogen gas and nitrogen gas in a separate fixation chamber, inter osing a liquid to separate said fixation c iamhers one from the other and to presents liquid surface in each fixation chamber, and subjecting said gas mix-' tures in the respective fixation chambers to an electric current of high tension.

19. The method of nitrogen fixation comprising mixing oxygen gas and nitrogen gas in one fixation; chamber, m ixing hydrogen gas and nitrogen gas in a separate fixation chamber,interposing a, liquid to separate said fixationchambers one from the other and to present a li ui'd absorbing surface in each fixation chain er, and subjecting said "as mixtures in the respective fixation chamhers to an electric current of high tension in which current of one polarity predominates.

20. The method of nitrogen fixation com prising subjecting oxygen gas and nitrogen gas in one fixation chamber and hydrogen gas and nitrogen gas in a separate fixation chamber. with an interposed liquid constituting a liquid electrode surface in each fixation chamber to an electric current of high tension in which current of one polarity predominates. I

21. The method of nitrogen fixation comprising subjecting oxygen and nitrogen in one fixation chamber and hydrogen and nitrogen in a separate fixation chamber with an interposed liquid to separate one fixation chamber from the other and to present a liquid absorbing surface in each chamber to an electric current of high tension.

22. The method of nitrogen fixation comprising subjecting oxygen and nitrogen in one fixation chamber and hydro en and nitrogen in a separate fixation cham er with an interposed liquid to separate one fixation chamber from the other and to present a. liquid absorbing surface in each chamber to an electric current of high tension, and maintaining said liquid at a substantially uniform temperature.

23. An electrolytic apparatus comprising a cell, an electrolyte in said cell, a gas chamher to confine a body of ect'rolyte and electrodes'one of which electrodes terminates in said body of s above and out of direct contact with said electrolyte.

24. The method of electro-chemical synthesis which. comprises passing an electrical current of high potential from one electrical terminal to another electrical terminal through an interposed body of as, one of said terminals being a nonmetal ic body of liquid adapted to absorb the synthetic product.

25. The method of electrochemical synthesis which comprises passing an electrical current of high potential from one electrical terminal to another electrical terminal through an interposed bod-y of gas, one of said terminals being an electrolyte adapted to absorb the synthetic roduct.

In testimony whereo I have aflixed my signature.

CASPER W. MILES. 

